KR840003254A - Method for preparing 6-substituted-s-triazolo [3,4-a] phthalazine derivatives - Google Patents

Abstract

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Description

Method for preparing 6-substituted-s-triazolo [3,4-a] phthalazine derivatives

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Claims (8)

4-substituted-1-hydrazino-phthalazine of the following general formula (II) was cyclized with a suitable cyclizing agent, and triazolo [3,4-a] phthalazine nucleus was prepared by a conventional method. A process for producing s-triazolo [3,4-a] phthalazine represented by the following general formula (I), characterized by optionally converting a substituent in the 3-position. In the above formula, R is a hydrogen element, hydroxyl group, (C ₁ -C ₆ ) alkyl group, phenyl group, or (C ₁ -C ₆ ) alkyl group, (C ₁ -C ₆ ) alkoxy group, chloro, fluoro, iodine, phenyl group, hydroxyl group, amino group ₁ selected from mono- and di- (C ₁ -C ₄ ) alkylamino groups, (C ₁ -C ₄ ) alkanoyl amino groups, piperidino groups, cyano groups, nitro groups, trifluoromethyl groups, carboxyl groups and carbamyl groups Or a phenyl group substituted with -3 substituents, or R represents a carbo- (C ₁ -C ₄ ) alkoxy group, a chloromercapto group, a (C ₁ -C ₄ ) alkylthio group, (C ₁ -C ₄ ) Alkylsulfinyl group, (C ₁ -C ₄ ) alkylsulfonyl group, general formula | Is an amino or substituted amino group of wherein R ₄ and R ₅ are each a hydrogen atom, (C ₁ -C ₄ ) alkyl group, (C ₁ -C ₄ ) alkenyl group or hydroxyl group, (C ₁ -C ₄ ) alkoxy group, Halogen atom, carboxyl group, cyano group, aminocarbonyl group, mono- or di- (C ₁ -C ₄ ) alkylaminocarbonyl group, (C ₁ -C ₄ ) alkoxycarbonyl group, (C ₁ -C ₄ ) alkoxythiocarbonyl group and (C ₁ -C ₄₎ substituted by one or two groups selected from alkylthio groups (C ₁ -C ₄₎ represent an alkyl group, or R ₄ and R ₅ is a substituted phenyl group, as well as part of the alkyl moiety as defined above, A phenyl- (C ₁ -C ₄ ) alkyl group or a substituted phenyl- (C ₁ -C ₄ ) alkyl group, and R ₄ and R _{5, which} are combined together with adjacent nitrogen atoms, are heteroatoms selected from nitrogen atoms, oxygen atoms and sulfur. Atom containing and optionally (C ₁ -C ₄ ) alkyl group, phenyl group, phenyl group substituted as above, hydroxyl group and carbo- (C ₁ -C ₄ ) alkoxy group may represent a saturated 4,5,6 or 7-membered cyclic hetero ring which may contain one or two substituents selected, wherein R is an alkoxy group or cycloalkoxy of the formula -OR ₆ Wherein R 6 represents a hydroxyl group, an amino group, a mono-di- (C ₁ -C ₄ ) alkylamino group, a (C ₁ -C ₄ ) alkoxy group, a halogen atom, oxo, carboxy, aminocarbonyl group, mono- or di- (C ₁ -C ₄₎ alkylamino group, (C ₁ -C ₄₎ alkoxycarbonyl, (C ₁ -C ₄₎ alkoxy group and a thio (C1-C4) alkylthio group selected from a one or two groups substituted (C ₁ -C ₄ ) alkyl group, R ₆ may also contain a hetero atom selected from nitrogen, oxygen and sulfur and optionally (C ₁ -C ₄ ) alkyl group, phenyl group, substituted phenyl group, hydroxyl group and carbo- (C ₁ -C ₄₎ may contain one or two substituents selected from an alkoxy group with a saturated 4, 5, 6 or Or a 7-membered ring heterocycle, or R ₆ is a (C ₁ -C ₄ ) cycloalkyl group optionally substituted with one or more hydroxyl groups and (C ₁ -C ₄ ) alkoxy group, R ₁ is a halogen atom, a hydroxyl group, (C ₁ -C ₄₎ alkylthio, (C ₁ -C ₄₎ alkylsulfinyl group, (C ₁ -C ₄₎ alkylsulfonyl group, a phenyl group, a phenyl group substituted as above, General formula R ₇ and R ₈ are an alkoxy group or a cycloalkoxy group of the formula -OR ₉ as defined above in R ₄ and R ₅ , wherein R ₂ and R ₃ are each a hydrogen atom, Halogen atom, (C ₁ -C ₄ ) alkyl group, (C ₁ -C ₄ ) alkoxy group and nitro group, where R ₂ and R 3 are equally hydrogen atoms and when R ₁ is a chloro atom, R is a phenyl group or 4-nitrophenyl group When R ₁ is a hydroxyl group, R cannot be a phenyl group and R and R ₁ are each -OR ₆ or -OR ₉ , wherein R ₆ and R ₉ are saturated hetero rings as defined above. And a hetero atom in this hetero ring cannot directly bond with an oxygen atom. The compound of claim 1, wherein R represents a hydrogen atom, a mercapto group, a (C ₁ -C ₆ ) alkyl group, a phenyl group substituted phenyl group and a carbo- (C ₁ -C ₄ ) alkoxy group, and the cyclizing agent is a trialkyl orthoformate salt. , Carbon disulfide and acid derivative of the following general formula. In the general formula, R represents a (C ₁ -C ₆ ) alkyl group, a phenyl group, a substituted phenyl group or a carbo- (C ₁ -C ₄ ) alkoxy group, X represents a chlorine atom or an -OR ″ group, wherein R ″ represents a methyl group or an ethyl group , Group, trifluoroacetyl group or ethoxycarbonyl group) The trizolo of formula (I) according to claim 1, wherein the corresponding 4-substituted-1-hydrazino phthalazine derivative is cyclized to disulfide carbon, and then R and R ₁ are mercapto groups. , 4-a] undergoes an oxidative chlorination reaction of phthalazine and the 3-chloro (or 6-chloro) substituent thus introduced Optionally substituted with an amine, an alkali metal alkoxide or cycloalkoxide MeOR ₆ of at least one of R and R ₁ is chloro or A process for the preparation of a compound of formula (I) wherein the amino or substituted amino group of or alkoxy group or cycloalkoxy group of formula -OR ₆ (wherein R ₄ , R ₅ and R ₆ are as defined above, Me is alkyl Cation of a ly metal. The method of claim 1, wherein the substitution corresponding 4-1-hydrazino-R is a mercapto group, a compound of general formula (Ⅰ) obtained by cyclization of phthalazine derivatives as carbon disulfide (C ₁ -C ₄₎ alkyl R is reacted with iodide (C ₁ -C ₄₎ alkylthio group to give the corresponding compound of formula (ⅰ) and if R is (C ₁ -C ₄₎ alkoxy group or a (C ₁ -C ₄₎ alkyl If a compound of the general formula (I), which is a sulfonyl group, is required, the compound obtained as described above is oxidized using a suitable oxidizing agent, wherein R is (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfonate. A process for preparing a compound of formula (I), which is pinyl or (C ₁ -C ₄ ) alkylsulfonyl. 4-substituted-1-hydrazino-phthalazine of the following general formula (II) is substituted with an aldehyde of the general formula R′-CHO, wherein R ′ is a (C ₁ -C ₆ ) alkyl group, a phenyl group, a substituted phenyl group or a carbo R is a (C ₁ -C ₆ ) alkyl group, characterized in that the hydrazine of the following general formula (III) produced by the reaction with (C ₁ -C ₄ ) alkoxy group) is cyclized to the required final product. And a phenyl group, a substituted phenyl group or a carbo (C ₁ -C ₄ ) alkoxy group. In the general formula, R ', R ₁ , R ₂ and R ₃ are as defined in claim 1. The corresponding compound of the general formula (I) wherein R ₁ is a halogen atom is selected from (C ₁ -C ₄ ) alkanediol R ₁ is (C ₁ -C ₄ ) alkylthio, formulated by treatment with amines or substituted amines or alkali metal alkoxy or cyclo alkoxides of formula MeOR ₉ | A process for preparing a compound of formula (I), wherein the amino or substituted amino group is an alkoxy group or a cycloalkoxy group of formula -OR ₉ , wherein R ₇ , R ₈ and R ₉ are as defined above Metal cation) 3-chloro-s-triazolo-phthalazine of the following general formula (VIII) or 6-chloro-s-triazolo-phthalazine of the following general formula (X) respectively corresponds to 3-hydroxy or 6- The intermediate obtained by conversion to a hydroxy derivative is reacted with an alkali metal hydride and then with a compound of formula XR or XR ₁ , respectively, wherein R is OR ₆ and R ₁ is OR ₆ . Method for preparing the compound. Reacting 3-hydroxy-s-triazolo-phthalazine of the following general formula (V) or 6-hydroxy-s-triazolo-phthalazine of the following general formula (VI) with alkali metal hydride each formula XR or compound and reacting with a compound of general formula electricity (ⅰ) R ₁ is oR ₆ and R ₁ is oR _9, characterized by a XR _1. ※ Note: The disclosure is based on the initial application.